FR2531967A1 - ELECTROACTIVE HETEROCYCLIC POLYMERS - Google Patents

Abstract

THE INVENTION RELATES TO HETEROCYCLIC ELECTROACTIVE POLYMERS. THE ELECTROACTIVE POLYMERS OF THE INVENTION ARE DOPED POLYMERS SUITABLE TO BE WORKED, INCLUDING RECURRING PATTERNS OF A SYSTEM OF UNSATURE CONDENSED HETEROCYCLIC CORES WITH 5 AND 6 CHAINS, CONDENSED WITH NITROGEN, WHICH ARE OBTAINED BY POLYM FROM PARTY CONTACT OF THE LATTER WITH ATOMS OR GROUPS OF DONORS OR ACCEPTING ATOMS MODIFYING CONDUCTIVITY. APPLICATION TO THE REALIZATION OF ELECTRONIC DEVICES.

Description

The present invention relates to

  electroactive organic polymers It has more

  particularly related to the association, with an organic polymer, of electroactivating agents called dopes in the prior art. Organic polymeric materials have recently been subjected to research to modify their electrical conductivity at room temperature, by reacting them with molecules of electron donors or acceptors. The molecules of donors or acceptors of electrons, generally referred to as N-type dopants and, respectively, p-type dopants in the prior art, can transform the organic polymeric materials such that these modified organic polymeric materials have a semiconductor-like electrical conductivity. and of

  metal type at room temperature Polyacetyl

  is an example of an organic polymeric material

  that the electrical conductivity at room temperature can be varied by several orders of magnitude above its insulating state by the incorporation of dope molecules (see U.S. Patent No. 4). Other examples of organic polymeric materials whose electrical conductivity at room temperature can be improved several orders of magnitude with respect to their insulating state by the incorporation of dope molecules are poly-p-phenylene. , polypyrrole, poly-1,6-heptadiyne and polyphenylenevinylene However, all examples

  mentioned above are examples of poly-

  organic matter that are totally insoluble or

  infusible and therefore can not work at all.

  Other examples of organic polymers whose electrical conductivity at room temperature can

  to be modified by means of dopes are poly (

  phenylene and poly-m-phenylene However,

  mentioned above, although they may be

  valueless in their original virgin state, undergo an irreversible chemical process when reacted with dopes that change their electrical conductivity

  at room temperature This irreversible chemical process

  These dopant-containing organic polymeric materials can be used in a state in which they can not be worked. When the doping agents are removed, these materials do not return to the chemical structure they originally had before being modified by the dopes. Sulfur polynitride, which is an inorganic material, is also considered a polymeric conductor. As in the case of the polymeric materials mentioned above, the sulfur polynitride can not

to be worked on him either.

  For a wide variety of applications to electronic devices, it is highly desirable to have electrically conductive organic polymer materials having a predetermined conductivity at room temperature that can be varied in

  a wide beach This beach should advantageously extend

  It is also desirable that the electrically conductive organic polymeric materials can be processed and, therefore, processed from the insulating state of the unmodified organic polymeric material to the highly conductive metallic state through the semiconductor regime. way to be able to achieve

  useful articles of all shapes and sizes

  Desired organic polymers that can be worked are those that can be easily shaped, shaped, molded, squeezed, cast, etc. into valuable articles, from the liquid state, i.e.

  molten state, the fluid glassy state or a solution

  after the polymerization reaction of the material

  organic polymer has been accomplished.

  We have just discovered an electroactive polymeric material comprising a modified organic polymer

  dope, whose electrical conductivity at the temperature

  The electroactive polymer is defined as being a polymer whose conductivity has been modified with acceptor or electron donor dopes so that it is greater than the conductivity in the state. Virgin

  of the polymer The organic polymeric electromaterial

  active is made from a virgin polymer, which is in itself entirely suitable for

  processed and which has excellent mechanical properties

  as well as being very stable to oxidative degradation, by modification of the polymer

  with electron donor dopes or dopes acceptable

  electrons The polymeric electro-organic matter

  is composed of repeating units of a system consisting of 5- and 6-membered fused unsaturated heterocyclic rings containing nitrogen and a

  conductivity More particularly, the electro-

  active is a positively charged polymeric backbone

  or negatively containing compensating ionic dopes

  charge carriers, that is to say ions whose charge

  is opposite to that of the polymeric backbone

  sufficient concentration of ionic dope is defined as the concentration which, when associated with

  polymer, causes a significant rise in

  tiveness, ie 1-0% or more. Recurrent patterns

  rents are diradicals The diradicals are attached directly to each other or may be related to

  to each other via joining patterns.

  A "joining pattern" is defined as any atom or group of atoms that can bind together the diradicals mentioned above in a polymer chain without impairing the reversibility of the oxidation or reduction or both. must be conjugated or must maintain the recovery of the orbital with the system

of heterocyclic rings.

  An N-type electroactive organic polymer is obtained by reacting the virgin polymer with

  Reducing Dopes or Electron Donors Dopes

  electrons induce n-type conductivity in the polymer by giving an electron to the polymer and reducing it to a polyanion, and the dope is oxidized to a polymer.

  Similarly, an organic organic polymer is obtained.

  p-type active by reacting the virgin polymer with

  electron-accepting oxidative dopes Suitable dopes

  electrons induce type 2 conductivity

  in the polymer by oxidation of the latter into a poly-

  cation and the dope is reduced to an anion The desired value of electrical conductivity at room temperature of the dope-modified electroactive organic polymer is pre-selected by adjusting the level of incorporation of the dopes to the virgin polymer Alternatively, the desired value The electrical conductivity of the ambient temperature of the dope-modified electroactive organic polymer is pre-selected by adjusting the reaction time between the virgin polymer and the dopes.

  highly selective and reversible modification of the

  electrical tivity at room temperature of the polymer

  may be by chemical or electrical means.

  The very selective and reversible modification of the electrical conductivity of the organic polymeric material containing a dope, as well as the ability to be

  worked and processed virgin polymer, is very

  desirable because the production of articles and

  useful positives such as primary and secondary batteries

  In addition, the materials described in the present invention can be used as active components in devices, devices and devices of the Schottky type.

  and items such as electronic display systems

  chromatic and photolithographic processes.

  Organic electroactive polymers are pro-

  modified by suitable dopes of poly-

  workable and processed virgin mothers consisting of recursive diradical units of a 5- and 6-membered fused nitrogenous aromatic heterocyclic ring system Polymers are composed of repeating diradical units derived from 5- and 6-membered fused nitrogen ring systems whose hetero atoms are in the 5-membered ring The 5-membered ring

  contains at least one nitrogen atom and a second hetero-

  atom selected from the group of O, S, Se, Te or N substituted atoms For n-type polymers, acidic proton substituents on the nitrogen atoms can not be present A diradical is defined as a molecule which at two unsatisfied positions, available for the attachment to the polymer chain The diradicals are optionally separated in the polymer chain by junction units It is also possible to incorporate hetero atoms such as nitrogen atoms ,

etc., at the hexagonal nucleus.

  Advantageous examples of nitrogen-containing 5- and 6-membered fused heterocyclic recurring units include: N-dialkyl substituted benzimidazoles; benzoxazoles; benzothiazoles; benzoselenazole; their substituted derivatives; and their mixtures. Advantageous examples of 5- and 6-membered heterocyclic repeating units, including the hexagonal ring

  contains one or more nitrogen atoms are the diradi-

  of the following compounds: oxazolo / -5,4-pyrimidine; oxazolo / -5,4-b pyridine; thiazolo / -4,5-d 7 pyrimidine; thiazolo / -4,5-d 7 pyridazine; thiazolo / -5,4-d-pyrimidine; thiazolol 4,5-b-pyridine; thiazolo [4,5-b] pyrimidine; thiazolo / -4,5-c-pyridine; oxazolo / -5,4-c-pyridazine;

  oxazolo / 4,5-b-pyridine, oxazolo-LT, 5-c-pyridine; thia

  zolo / 5,4-c_ 7 pyridine; oxazolo / -4,5-d 7 pyridazine; thiazolo / -5,4-c-pyridazine; oxazolo / -5,4-c-pyridine; Thiazolo / 4,5-b-pyrazine, their Substituted Derivatives, and Their Mixtures All of the 6-membered and 6-membered fused ring systems mentioned above are described in Ring Index, Second Edition and Supplements I, II and III,

  Patterson et al., American Chemical Society.

  The repeating units can be substituted on carbon atoms at the hexagonal ring with one or more

  substituents in order to adjust the electrical properties of

  morphological properties of the polymers derived therefrom.

  Suitable examples of substituents include the

U 53,967

  halogen, lower alkyl groups, lower alkoxy groups, aryl, etc. Recurring units may be intercalated with one or more joining units such as O, S, aryl, substituted aryl, alkenyl, thioalkenyl, thioaryl, etc. Joining units

  Preferred are phenyl units, -CH = CH and biphenylene.

  The joining patterns may be the same or different

  between adjacent recurring patterns in the chain

of the polymer.

  Heterocyclic polymers with 5 and 6 condensed chatons can be synthesized by polymerization

  by condensation of suitable monomers.

  transferred, known in the prior art, such as the displacement

  nucleophilic reaction of a dihalogenated compound with a salt

  disodium of a dimercaptan, can also be used.

  Electroactive polymers can be

  with repeating patterns of diradicals of posi-

  5 and 6-membered heterocyclic units

  substituted or unsubstituted diests and mixtures thereof.

  Diradicals can be bound by carbon atoms

  bone in 2,4 positions; 2.5; 2.6; 2.7; 4.6; 4.7; , 6 and 5.7, but preference is given to the bonds made at the 2.5 and 2.6 positions in the polymer. The ring system is numbered as follows: 3 X 1> 2 X where X is N and Z is chosen between O, S, Se, Te and NR 1 R 1 is a C 1 -C 6 lower alkyl, aryl, cycloalkyl or alkoxy group. R 1 is advantageously a phenyl, methoxy or methyl group. The R 1 group excludes H for

  n-type polymers. For example, a recurring pattern

  Appreciated is a 2.5-diradical illustrated as follows:

253) 967

  For example, a preferred recursive 2,6-diradical is illustrated as follows: Substituted diradicals are advantageously substituted

in positions 4 and 7.

  For electroactive polymers in which the hexagonal ring contains hetero atoms such as

  nitrogen atoms, the dúradical forming the recurring

  It can be represented by the formula: wherein Y is a fused hexagonal ring containing 1 or 2 nitrogen atoms selected from the group consisting of pyridine, pyrimidine and pyridazine rings.

  Diradicals are bound by the carbon atom in

  2 of the pentagonal ring and one of the carbon atoms

of the hexagonal nucleus.

* 8

  The polymer may be a homopolymer

  and their substituted derivatives or a copolymer of

  diradicals A homopolymer is defined as a poly-

  The copolymer is defined as being a polymer having different diradicals. In addition, the polymer is a copolymer if equal or different repeating diradicals are interspersed.

  In addition, recurring patterns

  For example, the patterns formed by the 2,5diradicals, head-to-head, that is, position 2 at position 2, then tail-tail, that is, position at position 5, or head-to-tail, ie position 2 to position 5 naturally, the recurring patterns can be interspersed with patterns of joining between

  head to tail 4 links or head-to-head or tail-to-tail.

  Alternatively, in the case of 6-membered and 6-membered rings whose hexagonal ring contains hetero atoms, "head-to-head" refers to a 5-membered ring linked to a 5-membered, "tail-to-tail" ring. "refers to a hexagonal ring linked to a hexagonal ring or" head to tail "means a pentagonal ring bonded to a hexagonal ring.

  The polymer is rendered electroactive by incorporating

  virgin polymer feed of an electron donor dope or an electron acceptor dope More particularly,

  the polymer is rendered electroactive by the addition of electro-

  trons with virgin polymer backbone (reduction) or by tearing of electrons from this backbone (oxidation) An electron donor dope gives an electron to the polymer, the latter being reduced to a polyanion and the dope being oxidized into a cation A acceptor dope of electrons tearing

  an electron to the polymer, the latter oxidizing into a poly-

  cation and the dope is thus reduced to an anion Alternatively, the polymer can be rendered electroactive by oxidation or electrochemical reduction In this case, a

  electron is torn off or added to the polymer by an elec-

  trode, and anions or charge-compensating cations, respectively, are incorporated into the polymer since the

253 '9 7

-9

support electrolyte solution.

  In both cases, the resultant electroactive polymer

  both consists of a charged polymer skeleton containing

  Charge compensating ionic dopes

  positively charged thinker may advantageously be a cation such as alkali metal ions, alkaline earth metal ions, Group III metal ions and organic cations such as R 1+ +, - N, R 1 X + + N, and Rxi is a straight chain or chain alkyl group

  branched C 1 to C 6 Mixtures of these dopes compensated

  These ionic dopes produce N-type conductivity when they are

  associated with a polynomeric polyanion reduced or negatively charged

tively.

  A negatively charged compensatory dope

  that is, an anionic dope may advantageously be an anion chosen from halogen ions, other ions such as As F 4, and preferably ions such as As F 6, C 104-, PF 6 503 CF 3, BF 4, NO 3, POF 4, CN, Si F 5-, Sb C 16, Sb F 6, HSO 4, organic anions such as CH 3 CO 2 (acetate), C 6 H 5 CO 2 (benzoate), CH 3 C 6 H 4 SO 3 (tosylate), etc. Mixtures of charge-compensating dopes can be used These ionic dopes produce a conductivity

  p type when associated with a polycation polycation

  oxidized or positively charged.

  The oxidized or reduced polymer has a charge opposite to that of the ionic dope The charges of the oxidized or reduced polymer and the ionic dope are balanced, so that the electroactive polymer is an electrically neutral system The association between the virgin polymer and

  electron donor dopes produces an electron polymer

  which has a conductivity of type n More parti-

  the reduction of the virgin polymer and the incor-

  poration of cationic charge-compensating dopes

2,319 7

  give a polymer which has a conductivity of the type

  n The combination of the virgin polymer with acceptable dopes

  In particular, the oxidation of the polymer and the incorporation of anionic charge compensating dopes produce a P-type conductivity polymer. The electroactive polymers of the invention are to the following formula: (Sd) {-FX + a R '-4 c (Y ç N lM (ld where y is 0 or 1; ba is 0 or 1; ca is 0 or 1; N is an integer between 1 and 1000, d is an integer between 1 and 2000, S is an integer equal to 1, 2 or 3; R is a fused ring system forming a 5- and 6-membered heterocyclic diradical containing unsubstituted or substituted nitrogen; R 'is the same as or different from R; X' is a joining moiety comprising a single atom or a group of atoms; Y 'is a joining moiety which is identical to X 'or which is different from it, and M is an atom or a group of atoms acting as ionic dopes Charge compensators whose electric charge is opposite to the charge presented by the repeating units of the polymeric backbone: (Sd) {R -) 4 (X ') a (R' c S n The repeating units form the polyanion or

  the polycation of the electroactive polymer.

  The R group forming a diradical is a substituted or unsubstituted 5-membered, fused hexagonal nitrogenous ring. The diradicals contain a nitrogen atom and a second heteroatom selected from N-R 1, O, S, Se and

  Te, in 1,2 or 1,3 positions in the pentagonal ring.

  Preferred condensed ring systems contain O and N or N-CH 3 and N, respectively, in the positions

1 and 3.

  More particularly, R and R 'are unsubstituted or substituted diradicates already mentioned or mixtures of diradicals which are linked to each other directly or via the joining units.

  X 'and Y' with bridging Bridges are advantageous

  gily forms in positions 2,5 or 2,6 for 1,3-heterocycles and in positions 3,5 or 3,6 for

  1,2- (i.e., iso) heterocycles.

  The joining patterns X 'and Y' may be chosen from the group comprising the units of formulas:

-0-; -S-; -NOT-; -CH = CH-;

  -C = C -, - CH = CH-CH = CH-; -CH = CH-S-CH = CH-; f 9>; -Go-CH = CH-; -CH-CH C -CH = CH-; R R 2 C Rv = c R V-; and -c R Vii = c Rvii; -Ar-N-Ar wherein R 1 has the definition given above and Rv, Rvi and Rvii represent H or a methyl group, a methoxy group, a halogen, and mixtures thereof; R 2 is a C 1 -C 4 lower alkyl group and a para-substituted phenyl group; and Ar is phenylene or biphenylene. Biphenyl, vinyl, R phenyl and -Ar-N-Ar junction groups are preferred joining units.

  The magnitude of N determines the physical properties

  electroactive polymer. Preferably, N has a

  value from 5 to 1000 when c is equal to O More

  N is calculated so that the polymer has a molecular weight of 10,000 or more. Workable films are formed with a polymer.

  electroactive agent in which N exceeds 50

  of the polymer should be between 500 and 500 000.

  A preferred molecular weight is equal to or greater than 000.

  The conductivity enhancement of the electron polymer

  active with respect to the conductivity of the polymer in the state

  blank is determined by d The value of d is not greater than

  less than 2 n Conductivity is high and adjusted by elevation of d Conductivity in the semiconductor region can generally be obtained with values d of about 5% of the n-value, for example

  d is 5 when N is 100.

  More particularly, the virgin polybenzothiazole has a conductivity of about 10 ohm 1 cm -1. Treatment of the polymer with a 0.5 M solution of sodium anthracenide gives a measured conductivity.

  about 4 x 10-2 ohm -1 cm -1 Electropolymers

  Preferred actives are doped polymers which have conductivities greater than about 1 x 10 10 ohm-1 cm 1, especially greater than 1 x 10-4 ohm -1 cm-1. Higher concentrations of the ionic compensator ion D

  charge raise the conductivity up to the conductive

  metal ticity Cationic or anionic dope M

  charge compensator is chosen between the

  born above, etc. M remains the same for all poly-

following favorite mothers.

  The groups R and R 'are equal or different.

  When a is equal to 1, b and c are equal to zero, R 'and Y' disappear and the polymer has the following formula:

253,967

  (L Sd) ER X 3 _ N LM: d A suitable example is poly-2,5- (p-phenyl)

  lene) -benzothiazole supplemented with an ionic

load.

  When a and c are equal to 1 and b is zero; Y 'disappears and the polymer responds to the formula: (i Sd)

-TR X 1-R 1 M

  A preferred polymer of this formula is poly-p-phenylene

  bibenzoxazole supplemented with a conductivity modifier.

  When a is zero and b and c are 1, X 'disappears and the polymer has the formula: (Sd) -RR' -Y 'N lM d A preferred polymer of this formula is poly-2,2' - (p-phenylene) -6,6 '-bibenzoxazole doped with a

  Another preferred polymer is poly-2,2 '-

  (m-phenylene) -6,6 '-bibenzoxazole The sulfide analogues, namely poly-2,2' - (p-phenylene) -6,6 '-bibenzothiazole and poly-2,2' - (m-phenylene) -6.6 "bibenzothiazole added with charge-compensating ionic dopes are also preferred When a, b and c are equal to zero, R ', XI, Y' disappear and the polymer has the formula (Sd) <Lln d Preferred polymers of this formulated are poly-2,5-benzoxazole, poly-2,6-benzothiazole and

  poly-2,5- (1-methyl) -benzimidazole, poly-2,6-pyri-

  dino / 3,2-d-7-oxazole) and poly-2,6-pyrazino-2,3-d-7-

  oxazole. A group 2,5 or 2,6-R or R 'is chosen from the diradicals which correspond to the formula: Rii

6

  wherein R 1 represents one to three substituent groups

  independently selected from H; an amino group disubsti-

  kill; an alkyl group having 1 to 4 carbon atoms; an alkoxy group having 1 to 4 carbon atoms; a group

  alkylthio having 1 to 4 carbon atoms; a cyclo-

  aliphatic having 5 or 6 carbon atoms; an aryl group having 6 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms substituted with one to three alkyl groups having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, one to three cyano groups, 1 to 3 halogen atoms, groups dialkylamino having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms; or a 5- or 6-membered nitrogenous unsaturated heterocyclic group. The nitrogen atoms of the above polymers can be quaternized by reaction with alkylating agents, for example dimethyl sulphate. The dotted lines indicate

  preferred positions 2.5 or 2.6.

  The term "alkyl" refers to alkyl groups

  Straight-chain and branched-chain

  are methyl, ethyl, propyl, isopropyl,

  butyl, isobutyl, sec-butyl and tert-butyl.

  The term "alkoxy" refers to the group R 10 in which R 1 is an alkyl radical. Suitable examples are methoxy, ethoxy, propoxy, isopropoxy,

  butoxy, isobutoxy, sec-butoxy and tert-butoxy.

253,967

'C

  The term "alkylthio" refers to examples such as methylthio, ethylthio, propylthio, isopropylthio,

  butylthio, isobutylthio, tert-butylthio and sec-butyl-

  thio. Suitable examples of cycloaliphatic groups

  ticks are cyclopentyl, cyclohexyl, 3-

  methylcyclopentyl, etc. The term "aryl" refers to an aromatic hydrocarbon radical such as phenyl, naphthyl, etc. Suitable examples of aryl groups substituted with a radical

  alkyl are 2-tolyl, mesityl, 3-isopropyl-

  phenyl, etc. Suitable aryl groups -substituted

  with an alkoxy radical are 1-methoxy-2-groups

  naphthyl, 3-n-butoxyphenyl, etc. Aryl groups

  Suitable cyano substituted compounds are 4-cyanophenyl, 4-cyano-1-naphthyl, etc. Suitable examples of aryl groups having a halogen atom

  include 4-fluorophenyl, 3-chloro-4-bromo-

  1-Naphthyl, etc. Suitable examples of aryl groups substituted with a dialkylamino radical are 3-dimethylaminophenyl, 6-diethylamino-2-naphthyl, etc. Suitable examples of substituted aryl groups

  with an alkylthio radical are 4-butylthio-

  phenyl, 3-methylthio-2-naphthyl, etc. Examples

  Suitable for pentagonal or hexagonal nitrogenous heterocyclic groups are 3-pyrrolyl, 4-pyridyl and the like.

  Suitable substituted diradicals are

  by the following polymers: poly-2,6- (4-methoxy)

  benzoxazole), poly-2,6- (5-ethylbenzoxazole); poly-2,5-

  (6-methylthiobenzoxazole); poly-2,6- (4-phenylbenzoxazole); etc. Naturally, other diradicals such as

  sulfur, nitrogen and selenium analogues according to the

  In addition, the substituted diradicals can be intercalated with joining motifs. An R or R'appreciated group is chosen between the diradicals of formula: ## STR1 ## in which Ri 1 denotes one or two substituents carried by the ring carbon atoms, as defined for R 1,

  and Y and Z have the definitions given above.

  Hereinafter, preferred electroactive polymers in which R and R 'are the same, b and c are 1, a is 0, Z is NR 1 in which R 1 is methyl, R 1 is H, Y is carbon,

  X is nitrogen and Y 'is m-phenyl or p-phenyl.

  Poly-2,2 '- (p-phenylene) -1,1'-dimethyl-5,5' -

  bibenzimidazole: 4? (-Sd): + IF N d X

CH 3 CH 3

  The polymer has a n-type reversible conductivity.

  Poly-2,2 '- (p-phenylene) -1,1'-dimethyl-6,6' -bi-

benzimidazole (Sd) E <* Sl "I In

CH 3 CH 3

* The polymer has a reversible conductivity of the n type and the p type.

  3-5 Poly-2,2 '- (m-phenylene) -1,1'-dimethyl-5,5' -

bibenzimidazole: -

(Sd) d | -i f 10 <i

CH 3 CH 3

  Poly-2,2 '- (m-phenylene) -1,1'-dimethyl-6,6' -

bibenzimidazole: + N I i (+ Sd) S

CH 3 CH 3

  The polymer has a reversible conductivity of the R-type

  Poly-2,2 '- (p-phenylene) -6,6' - (N, N'-dimethyl)

bibenzoxazolium) -metasulfate: Dd '

CH 3 O 5038 CH 3 OSO 3

  Other polybenzimidazole polymers

  are N-alkylated polybenzimidazoles described in US Pat. Nos. 3,509,108, 3,549,603 and 4,202,142.

  be alkylated by methods known in the art.

  Polymers are made conductive by exposure to

  oxidizing or reducing dopes or by electro-

doping chemicals.

  Recurrent oxygenated patterns appreciated, by

  benzoxazole, are obtained when R and R 'represent

  benzoxazole, b and c are 1, a is 0, Z is O, R 1 is H, Y is carbon, X is nitrogen, Y 'is m-, p-phenylene , Where is

  As indicated more particularly, recurrent patterns

  The following are the following: Poly-2,2 '- (p-phenylene) -5,5' -bibenzoxazole: N 5 S'5 N %% i-Sd) l + ji IU ld

  The polymer has a n-type reversible conductivity.

  Poly-2,2 '(p-phenylene) -6,6' -bibenzoxazole: N i (ï-Sd) n The polymer has a n-type and p-type reversible conductivity. Poly-2,2 '(m-phenylene) -5,5' -bibenzoxazole: d Poly-2,2 '- (m-phenylene) -6,6' bibenzoxazole: t (+ Sd) S The polymer has a conductivity reversible type R-1 9

  Poly-2,21- (N-methyl-p, p'-amïnodiphénylène) -6,61-

  bibenzoxazole: 1 1 The polymer has a reversible conductivity of the p type.

  Poly-2,21- (4,41-oxydiphenylene) -6,6 '-bibenzoxa

zole: 1 5

  Poly-2,21- (4,41-thiodiphenylene) -6,6 '-bibenzoxa

zole:

0 O "%

  1- (Sd) n -D-S (D N n) Poly-2,12- (4,41-diphenylene) -6,61-bibenzoxazole :: Sd) S 1: ci

NOT -

  Poly-2,21- (o-phenylene) -6,61-bibenzoxazole: 0%

"D- /

L 1-, I

  Poly-2,21- (3,5-furanediyl) -6,6 '-bibenzoxazole: * Sd f 57 4, \, O, 1 1 M id

% L (D

\\ 1 N L -J

  (+ Sd) -1 d (i-Ed) * Si id nr \ 1 -Md L (i-Sd) dd -J n Poly-2, 2 '(vinylene) -6,6' -bibenzoxazole O HH M id Poly-2,2 '(ethynylene) -6,6' -bibenzoxazole n L} Poly-2,2 (2,6-pyridinediyl) -6,6 'bibenzoxazole: ## STR1 ## Poly-2 2 (2,5-pyridinediyl) -6,6'-bibenzoxazol e (L Sd) in Poly-2,2 (2,5-oxadiazolediyl) -6,6-bibenzoxazole Poly-2,2 '- (2,5) -pyrazinediyl) -6,16 '-bibenzoxazole> N (Sd) F 4 S

0 O __ 1 _C -_L __

not

  The sulphurized and N-R 1 analogues of the poly-

  mothers above are also appreciated.

  Other preferred polymers are poly-2,2 '-

  (-P-diphenylene) -6,6 '-bibenzoxazole and poly-2,2' - (p-

  diphenylene) -5,5 '-bibenzoxazole, with dopes added

ionic charge compensators.

  A particularly preferred repeating unit corresponds to the formula: ## EQU1 ## This polymer has a reversible conductivity of the n type and of the p type when it is reduced or, respectively,

oxide.

  Preferred recurring sulfur units, namely benzothiazoles, are given below. The repeating units occur when R and R 'are benzothiazole, b and c are 1, a is 0, Z is S, R 1 is H, Y is carbon, X is

  nitrogen and Y 'is the m or p-phenylene group.

  Poly-2,2 '(p-phenylene) -5,5' -bibenzothiazole:

% '4',%

  The polymer has a n-type reversible conductivity. Poly-2,2 '- (p-phenylene) -6,6' -bibenzothiazole: Sd)

// ': N__A ->, N_ (Sd) the M.

  The polymer has a reversible conductivity of the n-type and the p-type. Poly-2,2 '- (m-phenylene) -5,5' -bibenzothiazole: ## STR2 ## Poly (2,2 ') - (m-phenylene) -6,6' -bibenzothiazole: NN (+ Sd) The polymer has a reversible conductivity of the p type. Hereinafter is mentioned a preferred electroactive polymer which is obtained when a, b and c are equal.

  at O and R is pyrido / -3,2-d 7 oxazole or pyrazino-

  / -2,3-d 7 oxazole: Poly-2,6- (pyrido / -3,2-d 7 oxazole): OW (; Sd) 1 S nn Poly-2,6- (pyrazino / 2,3- d 7 oxazole) dg 1 (+ t Sd) 1: Es -Oh (* Sd) rn A preferred electroactive polymer is indicated below wherein a and b are 0, c is 1, R and R are tailed tail-tail benzoxazole rings: Poly-2,2 '- (6,6' -bibenzoxazole): ## STR1 ## Preferred electroactive polymers in which a, b and c are 1, R and R 'are benzoxazole or benzothiazole, X' is O or S, and Y 'is m or p-phenylene: Poly-2,2' (p-phenylene) - 6,6'-oxybibenzoxazole: OO OO> 4-Sd I Ml 4 -N d

2531 967

  Poly-2,2 '- (p-phenylene) -6,6' -oxybibenzothiazole: (Sd) FO Ld n Poly-2,2 '- (m-phenylene) -6,6' -thiobibenzoxazole: S (Sd) MSW n Preparation of the polymer The starting material for the preparation of the

  The electroactive polymers of the invention consist of poly-

  and the copolymers comprising recurring units formed from a nitrogen-containing fused unsaturated heterocyclic ring system. The recurring units are advantageously substituted or unsubstituted 5- and 6-membered fused heterocycles in which a nitrogen atom is present. and another hetero atom are in the 5-membered ring. These polymers and copolymers are well known materials which have been synthesized in various ways. For example, benzimidazoles are described in US Pat. Nos. 3,509,108, 3,549,603 and 3,551,389. Nitrogen atoms may be substituted, for example N-alkylated,

  by methods known in the art.

  A high molecular weight polybenzimidazole can be prepared by the method of Vogel and Marvel described in Polym Sci, L, 511 (1969). According to this process, polybenzimidazoles are formed by melt polycondensation reaction of a compound. aromatic tetra-amine with various diphenyl esters

aromatic diacids.

  According to another variant, polybenzimidazoles may be prepared from aromatic tetramines

  or their hydrochlorides and aromatic dicarboxylic acids

253 '967

  condensation by polyphosphoric acid, described by Iwakura, Uno and Imai in

  J Polym Sci, part A, 2, 2605 (1964).

  The preparation of 2,5-polybenzimidazoles head-to-

  tail by self-condensation of 3,4-diaminobenzoic acid in the polyphosphoric acid used as a solvent is described by Imai, Uno and Iwakura in Macromol Chem,

83, 179 (1965)

  Polybenzimidazoles prepared in accordance with

  these processes must be N-alkylated prior to chemical doping.

  that or electrochemical of the present invention

  The alkylation reaction is well known in the art.

  and is carried out by means of alkylating agents

  such as alkyl halides, toky-

  alkyl lates and sulphates under basic conditions.

  For example, according to the procedure described by Kapodia and Patel in Macromol Sci, Chem, A 17 (3), 467 (1982), N-methylpolybenzimidazoles are

  formed by methylation of polybenzimidazole with sulphate

  dimethyl fate in the presence of sodium hydroxide.

  Because it is difficult to obtain an alkylation

  of a high molecular weight polymer by this process, the method recommended for the preparation of N-alkylpolybenzimidazoles involves the polymerization of a

N, N'-dialkylated monomer.

  For example, N-alkylated polybenzimidazoles were prepared by Korshak, Teplyakov and Fedorova, J Polym Sci, A-1, 9, 1027 (1971), by a melt polycondensation reaction of N, N-dialkyltetramines with diphenyl esters of aromatic dicarboxylic acids.

  Fully aromatic polybenzoxazoles can

  can be prepared by the method of Kubota and Nakanishi, Polymer Letters, 2, 655 (1964) The authors of this publication conducted a condensation reaction by

  steps of 3,3'-dihydroxybenzidine and iso-chloride

  In the second step, the polyamide films were dehydrated at 200-500 C until a fully aromatic polybenzoxazole was obtained. Another variant of this was process involves a one-step polycondensation reaction of 3,3'-dehydroxybenzidine or its hydrochloride with isophthalic or terephthalic acid in the acid

polyphosphoric at 150-215 C.

  The preparation of polybenzoxazoles by a reaction

  polycondensation, catalyzed by the polyphosphoric acid

  phoric, 3,3'-dihydroxybenzidine hydrochloride and an aromatic dicarboxylic acid is also described by Imai, Taoka, Uno and Iwakura in Macromol Chem,

83, 179 (1965).

  Homopolymerization of a trifunctional monomer such as 3-amino-4-hydroxybenzoic acid to obtain a 2,5-polybenzoxazole head-to-tail is described by

  Imai, Uno and Iwakura in Macromol Chem, 83, 179 (1965).

  In another variation, aromatic polybenzoxazoles were prepared by Moyer, Cole and Angos, J Polym Sci, 3, 2107 (1965), by polymerization in the state.

  melted 3,3'-dihydroxybenzidine with phenyl esters

  phthalic, isophthalic and terephthalic acids

and 5-chloroisophthalic acid.

  Aromatic polybenzothiazoles can be prepared from 3,3'-dimercaptobenzidine and diphenyl esters of aromatic dicarboxylic acids by solution polymerization in ethylaniline followed by isolation and heat treatment at 400 ° C. for 1 hour, as described by Hergenrother, Wrasidlo and Leviie in Polym Sci, part A, 3, 1665 (1965). In another variant of their process, high molecular weight polybenzothiazoles were obtained by a polycondensation reaction in one. alone

  step of 3,3'-dimercaptobenzidine and dicarboxylic acid

  aromatic lactic acid in the polyphosphoric acid used

as a solvent, at 200-250C.

  Polybenzothiazoles can also be prepared

  by a polycondensation reaction in solution of the

  3,3'-Dimercaptobenzidine hydrochloride and dicarboxylic acids in the polyphosphoric acid solvent used by Imai, Taoka, Uno and

  Iwakura, Macromol Chem, 83, 167 (1965).

  2,6-polybenzothiazole, head-to-tail homopolymer, can be synthesized from 3-mercapto-4-aminobenzoic acid hydrochloride or zinc salt.

  by a solution polymerization in polyhydric acid

  phosphoric according to the process of Imai, Uno and Iwakura,

Macromol Chem, 83, 179 (1965).

  The fused 5- and 6-membered heterocyclic ring polymers, in which the hexagonal rings contain nitrogen, may be produced by the above methods from pyridazines, pyridines

or appropriate pyrimidines.

  Production of a workable polymer After the polymerization, articles such as fibers, ribbons or self-supporting films can be obtained by casting a solution. The solution is obtained by dissolving the desired polymer in a solvent which consists of Sulfuric, formic acid, acid

  methanesulfonic acid or polyphosphoric acid The temperature

  The temperature of the solution ranges from about 25 to about 200 ° C. and is advantageously about 140 ° C., in particular 100 ° C. The polymers are coagulated into shaped solid bodies such as fibers, ribbons or self-supporting films in a basic bath. Coagulation For making self-supporting films, polymers are made from solutions containing about 2 to 25% of polymer

  dissolved in the solvent at concentrations which exceed

  10%, cast films acquire a morphology

  Anisotropic property The property of anisotropy favors the

  In the anisotropic direction, an amine, for example triethylamine, dissolved in a protonic solvent such as H 2 O and preferably ethyl alcohol, constitutes the coagulating bath. The bath is maintained at a temperature lower than the polymer dissolution temperature. in the solvent We usually choose the temperature

  ambient temperature as the working temperature for the coagulation bath.

  The shaped articles are dried High temperatures, usually 60 C, and reduced pressure

  speed up the drying process Elst drying

  followed until no more weight loss is observed. As an alternative, films are cast-in

  water, constituting the coagulating bath, and then they are neutral.

  The neutralized films are washed with water and dried at elevated temperatures,

  from 60 to 100 ° C, under reduced pressure.

  Modification of the conductivity of polymers

  After completion of the desired articles at

  polycondensed heterocyclic polymers, by the procedure described above, the articles are rendered electroactive, for example by chemical or

  electr 6 chemical -The articles can be made electro-

  active in an atmosphere which is inert to the polymer and the dope by contacting them with suitable conductivity modifiers, i.e. dopes An inert atmosphere is defined as an atmosphere which does not react with the polymer, the dope or the electroactive polymer For example, the atmosphere may consist of argon, helium and nitrogen, etc. The inert liquid medium must be capable of wetting and swelling the polymer but not of reacting with it. The doping may also be carried out in an inert liquid medium such as tetrahydrofuran, acetonitrile, etc. The dopes may be oxidizing molecules or accepting electrons or reducing molecules or giving up electrons Both types of dopes may be in the form of gas or vapors, pure liquids or

  preferably liquid solutions of oxygen and

  are excluded during and after the doping process

  conductive polymers tend to deteriorate

  der, that is to say to lose their conductivity, when

are exposed to it.

  For example, the polymer may be contacted with alkaline naphthalides or alkaline anthracenides

  such as sodium naphthalide, potassium naphthalide

  sium or sodium anthracenide in solution in the tetra-

  hydrofuran The concentration of the

  range from about 0.001 to about 1 M and

  from about 0.01 to about 0.5 M in THF or other suitable solvent. Other doping methods are taught in US Pat.

No 4 204 216.

  The acceptor or electron donor dopes oxidize or reduce the polymer and are incorporated as charge compensating ionic dopes. The incorporation of the dopants into the polymer can be observed by a color change of the polymer as well as by an improvement of the conductivity. For example, a yellow, orange or brown virgin polymer film takes on a metallic green, blue or black color when doped, and the

  measured conductivity increases by several orders of magnitude.

  Alternatively, the polymers can take their conductive forms by oxidation or reduction, using electrochemical techniques in this process, which is referred to herein as electrochemical doping.

  memory, the polymer is immersed in a solution

  Suitable electrolyte and it forms one of the electrodes of an electrochemical cell By passing an electric current in this cell, the polymer is reduced (or oxidized, depending on the direction of flow of the current) and cations (or anions ) charge compensators from the electrolyte

  of support, are incorporated into the polymer. This doping accom-

  also the characteristic color change described above. Thus, the polymer can be doped with

  electrochemical pathway with any suitable ion-

  charged in the electrolyte solution.

  Electrolyte solutions are formed of a salt dissolved in a solvent Suitable solvents include

  acetonitrile, tetrahydrofuran, 2-methyltetrachloride,

  hydrofuran, propylene carbonate, dimethylfor-

  mamide, dimethylsulfoxide, etc. Other electrolytes are specified in the United States patent application

  N 334 509 filed on 28 December 1981 Cations

  Examples of suitable anions include Cl, Br, Cl O 04, BF 4 and degree of doping can be easily adjusted by adjusting the amount of electrochemical charge injected into the polymer, either by adjusting the magnitude of the current used (galvanostatic charge), or by adjusting the potential of the polymer electrode

  relative to the reference electrode (potential charge

  static). The electrochemical doping method described above is completely reversed. The polymer can be "dedoped" and returned to its neutral, non-conductive initial state by simply passing a current of opposite sign to that used for the process. Doping When the dedoping is complete, the polymer takes its color

  Thus, for example, a poly-2,2 '- (p)

  reduced phenylene) -6,6 '-bibenzoxazole can be completely reoxidized to its non-conductive neutral form and the charge compensating cations incorporated during the electrochemical reduction process are removed

  of the article during electrochemical reoxidation.

  After describing the production processes and the fundamental polycondensed heterocyclic systems, the following examples which illustrate the invention are described.

  In a non-restrictive way, modifications which would be obvious

  for those skilled in the art are considered as entering

in the context of the invention.

Example 1

  Preparation of 2,5-polybenzoxazole Synthesis of the monomer Preparation of 3-amino-4-hydroxybenzoic acid 3-Amino-4-hydroxybenzoic acid was prepared according to the procedure described by Imai,

  Uno and Iwakura in Macromol Chem, 83, 179 (1965).

  50 g (0.362 moles) of p-hydroxybenzoic acid were added to 200 ml of nitric acid diluted 1: 6 with water in a 500 ml three-necked flask equipped with a magnetic stirrer. A reflux condenser and a heating jacket The reactants have

  stirred at room temperature for half a minute

  hour and at reflux for 16 hours The product was collected by filtration, washed with water and dried under vacuum. The yield of 3-nitro-4-hydroxybenzoic acid was

  50.9 g, that is to say 77% of the theory.

  g (0.109 moles) of 3-nitro-4-hydroxy-acid

  benzolque were suspended in 200 ml of absolute ethanol in a Fisher-Porter pressure-resistant bottle, equipped with a magnetic stirrer 2.4 g of 5% palladium on carbon were added and the bottle was put in communication with a gas collector The reaction bottle was purged with nitrogen and hydrogen was introduced to a pressure

  0.28 M Pa from a hydrogen storage tank.

  350 ml gene The hydrogenation reaction was conducted for 16.5 hours at room temperature, under constant pressure. The catalyst was removed by filtration on

  "Celite" and the filtrate was concentrated to dryness with evaporation

  rotat 4 The product was recrystallized from 85 ml of hot HCl 2 N The yield was 17.5 g, 36%

of the theory.

  Analysis: C (%) H (%) N (%) Calculated for C 7 H 803 N Cl 44.35 4.25 7.39 Found: 44.50 4.18 7.46

mp 271-275C (decomposition).

  Then the polymer was prepared according to

  in the mode of operation of Imai, Uno and Iwakura (see above).

  108.4 g of polyphosphoric acid (Aldrich) were charged into a 250 ml 3-neck flask equipped with a mechanical stirrer, a reflux condenser and a nitrogen inlet. The flask was installed in a bath

  of oil and heated at 200 ° C. under a nitrogen atmosphere.

  2.9 g (0.015 mole) of hydrochloride was slowly added.

  of 3-amino-4-hydroxybenzoic acid The polymer reaction

  was carried out at 200 ° C. for 4 hours.

  The hot polymer solution was poured into water, where it coagulated to form a fibrous spindle. The filtered polymer was neutralized in 5% Na HCO 3 solution for 15 hours and washed well with water. After drying under vacuum, 1.2 g (67% of the

polymer theory.

  Analysis: C (%) H (%) N (%) Calcd for (C 7 H 3 NO) 71.80 2.58 11.96 Found: 68.28 2.63 11.41

Example 2

  Preparation of 2,6-polybenzothiazole Synthesis of monomer Preparation of 3-mercapto-4-aminobenzoic acid This monomer was prepared according to the procedure of Imai, Uno and Iwakura, Macromnol Chem, 83,

179 (1965).

  56.0 g (0.408 mol) of p-aminobenzoic acid and 120 g of ammonium thiocyanate dissolved in 670 ml of glacial acetic acid in a 3-necked flask

  of 2 1, equipped with a reflux condenser, a desiccant tube

  a magnetic stirrer and a dropping funnel.

  24 g of bromine in 234 ml of glacial acetic acid was added dropwise after half an hour.

  stirring at room temperature, the reaction mixture

  nel was filtered from 2-amino-6-carboxylic acid hydrobromide

  benzothiazole crystallized at rest The product was recrystallized from a mixture of water and HCl to give

  21.6 g (23% yield) of 2-amino-6-hydrochloride

carboxybenzothiazole.

  g (0.087 mole) of 2-amino-6-carboxybenzoate

  Thiazole was dissolved in hot solution of KOH in 100 ml of water. The solution was cooled and neutralized at pH 7 with 85 ml of concentrated HCl, while cooling with ice. The neutralized solution was filtered solution of 20 g of Zn C 12 in 50 ml of water 25 ml of acetic acid were added and the product was collected by filtration The crude product was recrystallized from 300 ml of concentrated HCl 1 NHCl

  giving 13.5 g (76%) of crystalline monomer.

  Analysis: C (%) H (%) N (%) Calculated 40.88 3.92 6.81 Found: 40.99 3.73 6.83 Next, the polymer was prepared from the above monomer according to to the aforementioned method

from Imai, Uno and Iwakura.

  2.9 g (0.014 mol) of 3-mercapto-4-aminobenzoic acid hydrochloride were added to 107 g of polyphosphoric acid (Aldrich) in a 250 ml 3-neck flask equipped with a reflux condenser. The flask was immersed in an oil bath at 180 ° C. and the reaction was continued for one hour. The polymer was coagulated in water, neutralized in a 5% aqueous solution of NaHCO 3 and thoroughly washed and dried. obtained

1.8 g (95%) of polymer.

  Analysis: C () H (%) N (%) S (%) Calculated: 63.14 2.27 10.52 24.07 Found: 59.58 2.29 9.81 20.8

  Nsp = 0.145 (0.2 g / 100 ml of H 2 SO 4 at 30 C).

Example 3

  Poly-2,2 '- (p-phenylene) -6,6' -bibenzoxazole Synthesis of monomer Preparation of o-dihydroxybenzidine Odihydroxybenzidine was prepared from o-dianisidine according to the method of Burkhardt and Woold, J Chem Soc , 1929, 50 g of odianisidine dihydrochloride was refluxed with 475 ml of HI (47%) under a nitrogen atmosphere for 48 hours; the excess of HI was distilled off in a water-bath

  and a saturated solution of sodium acetate was added.

  The white precipitate was washed with ethanol and then boiled with 30 ml of ethanol to remove the unreacted starting material. The product was collected by filtration, washed and dried. The product has been recrystallized twice in a

mixture of water and HCl.

Analysis: Calculated for: C (%)

H (%) N (%)

  C 12 H 403 N 202 C 12 49.84 4.88 9.69

  Found: 49.80 4.80 9.55 Next, the polymer was prepared from the above monomer according to the Imai method,

  Taoku, Uno and Iwakura, Macromol Chem, 83, 167 (1965).

  54 g of polyphosphoric acid (Aldrich) were heated at 200 ° C. under a nitrogen atmosphere in a 250 ml 3-neck flask equipped with a mechanical stirrer, a reflux condenser and a nitrogen inlet. 2.4242 g (9.352 mmol) of dihydroxybenzidine dihydrochloride was added slowly to prevent foaming.

  1.5545 g (9.357 mmol) of terephthalic acid were then added.

  The sublimation was continued at 200 ° C for 2 hours. The polymer was coagulated in water to form a fibrous spindle. The polymer was filtered and neutralized in 5% Na HCO 3 solution for 16 hours, washed.

  The polymer yield was quantitative.

  Analysis: C (%) H (%) N (%) Calculated for: (C 20 H 1002 N 2) n 77.41 3.25 9.03 Found: 67.87 3.07 7.91

  Nsp = 0.150 (0.2 g / 100 ml, H 2 SO 4), 30 C.

Example 4

  Preparation of Films and Yarns A 4.4% (by weight) solution of poly-2,2 '- (p-phenylene) -6,6' -bibenzoxazole (Example 3) in polyphosphoric acid was prepared by dissolving 1.32 g of polymer in 28.55 g of polyphosphoric acid at 1500 ° C. under a nitrogen atmosphere Self-supporting films were cast from this solution and coagulated in water

  or in a 10% solution of triethylamine in ethanol. Similarly, platinum wires for electro-

  chemicals were coated with the polymer solution and

  the coatings were coagulated in the baths above.

  After coagulation in water, the films were neu-

  in 5% Na HCO 3 solution. After neutralization, the films were washed well and

dried under vacuum at 70 ° C.

Example 5

  Chemical doping of 2,6-polybenzothiazole A transparent brown film of the polymer of Example 2 was placed in a vessel in an anhydrous chamber containing a dry atmosphere of argon. After 30 minutes, the vessel was poured into the vessel. 0.1 M sodium naphthalide solution in dimethoxyethane The film reacted immediately with a darkish black color. The doped film was subjected to a standard 4-point conductivity measurement on a sample. The 4-point test method was described in U.S. Patent Application Serial No. 370,231 filed April 22, 1982 The measured conductivity of the polymer was 0.04 ohm cm.sup.-1. When exposed to air, the dark color disappeared instantly and the polymer has returned to its original color The infrared spectrum has been the same for the initial undoped film and the doped film exposed to air

* infrared spectrum of dark film doped with sodium naphthalide

  that was opaque, without transmission between 4000 and 200 cm 1, which indicates a metallic behavior This test shows that the doped polymer films are, so on

  stakeholder, good conductors of electricity.

Example 6

  Electrochemical Doping of Example 3 A 12.7 cm platinum wire was coated with a thin film of the polymer of Example 3 by immersion of

  in a 5% solution of the polymer in the polybasic acid.

  Phosphoric The film coated wire was coagulated in water, neutralized in 5% sodium bicarbonate solution, washed with water and dried in a vacuum oven at 60 C. The polymer coated wire was connected to an Applied EG and G Princeton Appliance including a universal programmer and a device

  potentiostatic / galvanostatic, with a recorder.

  The end of the polymer-coated yarn was then immersed in a 0.1M solution of tetraethylammonium tetrafluoroborate in acetonitrile. A linear potential sweep ranged from 0 to -2.5 V relative to the reference electrode. calomel was applied to the polymer coated wire A cathode current began to flow when the potential reached -1.7 V, and two peaks of cathodic current were observed at -2.0 V and -2.4 V This indicates sequential absorption

  of two electrons by repeated polymeric units.

  At this stage, the polymer is negatively charged and contains tetraethylammonium cations as charge compensating dopes. In fact, the polymer has been rendered electroactive by the application of a potential of about -2 V in the presence of a solution of electrolyte capable of supplying ions of the charge compensating dope By reversing the direction of the potential sweep, two anodic current peaks have been observed at substantially the same voltages This is the index

  reversible elimination of the two electrons previously

  injected into the polymer This procedure brings

  the polymer in its undoped, uncharged state.

Example 7

  Electrochemical doping of self-supporting films of Example 4 A 12.7 mm diameter disk of film of the polymer of Example 4 with a thickness of 25.4 μm was

  dipped in an electrolytic solution of tetrafluoro

  0.1M tetraethylammonium borate and held tight against a gold-plated flat electrode with a thin "nylon" cloth. This electrode was connected to the same apparatus as that of Example 6 As the potential of the electrode coated with gold in contact with the polymer reached

  the negative value of -1.7 volts, the polymer film trans-

  parent initially pale brown became dark and opaque.

  After maintaining the potential of the electrode at -2.2 volts relative to the calomel reference electrode for about 5 minutes, the film was removed from the electrochemical cell, rinsed with acetonitrile to remove the solution of excess electrolyte and allowed to dry in an argon atmosphere Conductivity measurement on a 4-point sample of the resulting electrochemically doped film reveals a conductivity of 0.05 ohm 1 cm 1 In fact, the polymer film was doped to a conductive state by applying a potential of -2.2 volts in the presence of an electrolyte solution. This corresponds to a reduction of the polymer to an n-type conductive state.

Example 8

  Electrochemical doping of a 2,6-polybenzothiazole A platinum wire was coated with a thin film of 2,6-polybenzothiazole (Example 2) using the procedure described in Example 6 The wire was immersed in a solution of 1.5 M lithium perchlorate in tetrahydrofuran and connected to the electrochemical apparatus described in Example 6 A potential varying between 0 and -3.0 volts' relative to the calomel reference electrode was applied With the polymer-coated wire When scanning the potential below -1.5 volts, a cathode current was observed which reached a maximum between -1.9 and -2.1 volts. When the differential scanning was reversed, observed an anodic current peak

at -1.7 volts.

  This behavior indicates initial resistance to current flow followed by rapid absorption

  electrons, from which an electro-

  charged active containing lithium ions as dopes coepen-

  In fact, the polymer was rendered electroactive by the application of a potential of about -2 volts in the presence of an electrolyte solution capable of

  to bring a charge compensating dope.

  In the potential scan of the polymer-coated wire in the positive direction, a positive anode current of + 1.2 volts was observed, reaching a maximum of about + 1.4 volts with respect to the calomel reference electrode. indicates that the polymer has been oxidized

  taking a cationic form containing ions

  BF 4 from the electrolyte solution.

  When the potential sweep was reversed, a peak of cathodic current was observed at the same voltage, indicating that the polymer had been reduced by reduction.

E 531967

  to its initial neutral form Indeed, the polymer has been

  rendered electroactive by applying a potential of

  Viron + 1.5 volts relative to the calomel reference electrode in the presence of an electrolyte solution capable of providing charge-compensating doping ions.

Example 9

  Preparation of poly 2,2 '- (m-phenylene) -6,6' -bibenzoxazole The polymer was prepared according to a modified version of the process of Imai, Taoka, Uno and Iwakura,

  Macromol Chemistry, 83, 167 (1965).

  2.0825 g (7.202 mmol) of dichlorhydrin were charged with

  r-dihydroxybenzidine drate and 50 g of polyphosphoric acid

  phloric acid (Aldrich) in a 250 ml 3-neck flask equipped with a mechanical stirrer, a reflux condenser

  and a nitrogen inlet The solution was stirred at room temperature

  at room temperature for 6 hours and at 60 ° C. for about 16 hours. Then, the temperature was raised to 110 ° C. and 1.1969 g (7.205 mmol) of isophthalic acid and 30 g of polyphosphoric acid were added. The polymerization temperature The reaction was continued at 165 ° C. for 12 hours, followed by a period of 12 hours at 195 ° C. The hot solution of polymer was poured into 2 liters of water. The coagulated polymer formed a fibrous spindle which disintegrated into a powder when stirring was continued. The polymer was filtered and neutralized for about 16 hours in a 5% sodium bicarbonate solution. neutralization, the polymer was washed with water and extracted

  continuously with methanol for about 16 hours.

  After drying under vacuum, 2.04 g (yield

  91.5%) of brown colored polymer.

  Analysis: C (%) H (%) N (%) Calculated for (C H O N) n 77.41 3.25 9.03 Found: 20 O 2 2 74.01 3.34 8.74 253 i 967

Example 10

  Preparation of Films and Yarn Self-supporting films of the polymer of Example 9 were cast from a 5% solution of the polymer in methanesulfonic acid at room temperature. The films were cast on glass plates which were immersed in a 10% solution of triethylamine in ethanol for coagulation. The neutralized films were separated from the glass plates and washed until exhaustion was achieved. The films were dried under vacuum at 700 ° C platinum coated yarns for

  electrochemical studies, were prepared in the same way.

Example 11

  Electrochemical Doping The polymer coated wire of Example 10 was connected to an Applied Research Apparatus E G and G Princeton comprising a universal programmer and a

  potentiostatic / galvanostatic device with

  The polymer-coated end of the wire

  was then immersed in a 0.1M solution of tetra-

  tetraethylammonium fluoroborate in acetonitrile.

  A linear potential sweep, ranging from 0 to 1.8 V relative to the calomel reference electrode, was applied to the polymer coated wire. Anode current began to flow when the potential reached + 1.2 V and a maximum of anodic current was observed at + 1.5 V. At this stage, the polymer is positively charged and contains tetrafluoroborate anions as compensating dopes

  In fact, the polymer was made electro-

  active by the application of a potential of about 1.5 volts in the presence of an electrolyte solution capable of providing

  charge-compensating doping ions In the inversion

  In the direction of the potential sweep, a cathode peak approximately at the same voltage was observed.

  injection of an electron previously torn from the polymer.

  This procedure brings the polymer back to its original state

undoped and unfilled.

Example 12

  Preparation of 3,3 '-poly-2,2' - (p-phenylene) Synthesis of diamino-4,4'-dihydroxybiphenyl monomer ml of 70% nitric acid was added dropwise, using a light bulb to bromine, to a solution of 60 g (0.322 mol) of p, p, '' - biphenol in 1 liter of acetic acid in a 2-necked 3-neck flask equipped with a mechanical stirrer and a reflux condenser The reaction flask was ice-cooled. When the addition was complete, the reaction mixture was allowed to warm to room temperature. The yellow product was filtered, washed with acetic acid and water. and dried under vacuum at 70 ° C., giving 67.1 g (85.3% yield) of crude product. The 3,3'-dinitro-4,4'-dihydroxybiphenyl was recrystallized.

in acetic acid.

  6.8 g (0.028 mole) of 3,3'-4,4'-dinitropheniline

  dihydroxybiphenyl were hydrogenated on 1 g of 5% palladium on carbon in acetic acid under

  hydrogen pressure of 0.35 M Pa

  nation was conducted for 2.1 hours at room temperature 3,3'-diamino-4,4'-dihydroxybiphenyl was

  isolated in a yield of 54% in the form of dichlorhydrin

  drate. Analysis: (%) H (%) N (%) Calculated for C 12 H 14 N 202 c 2 49.84 4.88 9.69 Found: 48.84 4.97 9.28

  Then, the polymer was prepared according to

  in the procedure of Example 9 using 2.055 g.

  (7.107 mmol) 3,3'-diamino-4,4'-dihydrochloride

  dihydroxybiphenyl, 1.1866 g (7.143 mmol) of terephthalic acid and 80 g of polyphosphoric acid. The polymer was isolated as a greenish brown powder. Analysis: C (%) H (%) N (%) Calculated for (C 20 H 1002 N 2) n 77.41 3.25 9.03 Found 72.89 3 23 8.19 j - The polymer had the formula :

3

Example 13

  Electrochemical doping of self-supporting films of Example 4 A polymer film of Example 4 was held without tightening against a platinum flat electrode in the same electrolyte solution as in Example 4 After maintaining the potential of the electrode at + 1.7V relative to the calomel reference electrode for 12 minutes the polymer was removed from the electrochemical cell, rinsed with acetonitrile, and then allowed to dry.

  four-point conductivity measurement of the electro-

  resulting chemically doped gave a conductivity of 2.3 x 10-2 ohm-1 cm 1 Indeed, the polymer film was doped to a conductive state by application of a potential of + 1.7 volts in the presence This corresponds to an oxidation of the polymer to a p-type conductive state.

Example 14

  Electrochemical doping of poly-2,2 '- (m-phenylene) -6,6' -

  bibenzoxazole A 12.7 mm diameter disk of a film of the polymer of Example 10 with a thickness of 25.4 Nm

  was immersed in an electrolytic solution of tetra-

  0.1 M tetraethylammonium fluoroborate in acetonitrile and held tight against a flat platinum electrode with a thin "nylon" cloth This electrode was connected to the same apparatus as that described in FIG. Example 6 The potential of the platinum electrode in contact with the polymer was raised to +2 V relative to the calomel reference electrode and maintained at this value for 8 minutes. Then, the film was removed from the electrochemical cell , rinsed with acetonitrile to remove any excess electrolyte solution and allowed to dry in an argon atmosphere.

  four-point conductivity measurement of the electro-

  resultant chemically non-dop revealed a conductivity of 2 102 ohm 1 cm 1 Indeed, the polymer film was doped to a conductive state by the application of a

  potential of + 2 V in the presence of an electro-

  This corresponds to the oxidation of the polymer to a conductive state of the p type.

Example 15

  Preparation of poly-2,2 '- (p-phenylene) -6,6' -bibenzothiazole Synthesis of the monomer R-Dimercaptobenzidine was prepared by the procedure described in Houben-Weyl, Methoden der.

  Organischen Chemie E. Miller Ed, IX, 39 (1955).

  g (0.271 moles) of benzidine (Fluca) was dissolved in 670 ml of acetic acid in a 2-neck 3-neck flask equipped with a mechanical stirrer and reflux condenser 165 g (2.1 moles) NH 4 SCN were added forming a large precipitate.

  dropwise 32.4 ml of Br 2 in 250 ml of acetic acid.

  to the reaction mixture with stirring.

  Stirring was continued at room temperature for about 16 hours. The yellow precipitate was then filtered off and washed with acetic acid. The 2,2'-diamino-6,6'-bibenzothiazole I was recrystallized from 0.degree. 1 water with 34 ml of

  HC 1, by acidification with concentrated hydrochloric acid.

  2,2'-diamino-6,6 '-bibenzoxazole was added to a solution of 54 g of KOH in 372 ml of water and refluxed under nitrogen for 3 hours. during cooling was isolated by filtration under nitrogen and recrystallized from a mixture of HCl and water 1: 2. 44.6 g (-51%) of

  r-dimercaptobenzidine dihydrochloride.

  Analysis: C (%) H (%) N (%) S (%) Calculated for C 12 H 4 N 252 C 12 44.86 4.39 8.72 19.96 Found: 45.43 4.33 8, 80 20.00 Synthesis of the polymer 2.4721 g (7.6943 mmol) of r-dimercaptobenzidine dihydrochloride and 1.5631 g (7.6992 mmol) of terephthaloyl chloride (Aldrich, recrystallized) in 44 g of polyphosphoric acid (Aldrich, 85%) were mechanically stirred and heated under nitrogen as follows: 60 C for about 16 hours, 165 C in 5 hours, 165 C for 12 hours and 195 C for 12 hours Mixing in progress of polymerization

  took a dark brown color and became very viscous.

  It was diluted with 60 g of PPA and then poured into 1 liter of water. The coagulated polymer was ground in a mixer, neutralized in a 5% solution of Na HCO 3 and washed with water. Next, it was transferred. in a Soxhlet extractor in which it was extracted with methanol for about 16 hours After drying under vacuum at 70 ° C.,

  collected 2.53 g (90%) of poly-2,2 '- (p-phenylene) -6,6' -

  bibenzothiazole. Analysis: C (%) H (%) N (%) S (%) Calculated for: C 20 H 10 H 25270,15 2.94 8.18 18.73 Found: 69.27 2.95 8.25 18 40

Example 16

  Chemical doping of poly-2,2 '- (p-phenylene) -6,6' -bibenzo

thiazole -

  A transparent brown film of the polymer of the example

  15 was placed in a container in an anhydrous chamber under a dry argon atmosphere after 30 minutes.

  a 0.1 M solution of sodium naphthalide in dimethoxy

  ethane was poured into the container The film reacted immediately by taking a metallic blue color

  doped film was subjected to a conventional measurement of

  The four-point sample method is described in U.S. Patent Application Serial No. 370,231 filed April 22, 1982. The measured conductivity of the

2531967,

  polymer was 0.02 ohm 1 cm 1 By exposure to air, the dark color disappeared instantly and the polymer resumed its original color The infrared spectrum was the same for the initial undoped film and for the doped film exposed to air The infrared spectrum of the sodium naphthalide-doped dark film was opaque, with no transmission between 4000 and 200 cm 1, which indicates a metallic behavior. This test shows that the doped polymer films are surprisingly

  good conductors of electricity.

Example 17

  Electrochemical Doping of Example 15 A 12.7 cm platinum wire was coated with a thin film of the polymer of Example 15 by dipping the wire into a 2.5% solution of the polymer in the acid. methanesulfonic The film coated wire was coagulated in water, neutralized in 5% sodium bicarbonate solution, washed in water and dried under vacuum

at 60 C.

  The polymer coated wire has been connected to an Applied Go et Go Princeton Research Appliance, including a universal programmer and a device.

  potentiostatic / galvanostatic with recorder

  wire-coated polymer tremit was then submerged

  in a 0.1M solution of tetrafluoroborate tetrafluoroborate

  ethylammonium in acetonitrile A sweep of

  A linear current varying from 0 to -2.5 V with respect to the calomel reference electrode was applied to the polymer-coated wire. A cathode current began to flow when the potential reached -1.5 V and two maximums of cathodic current were observed at -1.7 and -2 V This indicates sequential absorption

  of two electrons by the repeated polymeric units.

  At this stage, the polymer is negatively charged and contains tetraethylammonium cations as compensating dopes

  In fact, the polymer was made electro-

  active by the application of a potential of about -2 V in the presence of an electrolyte solution capable of providing ions of the charge compensating dope When the direction of the potential sweep was reversed, two anodic current peaks at about the same voltages This indicates the reversible elimination of the two electrons previously injected into the polymer This procedure returns the polymer to its initial state

undoped and unfilled.

Example 18

  Preparation of poly-2,2 '- (m-phenylene) -6,6' -bibenzothiazole

  2.5153 g (7.8283 mmol) of r-dimercaptobenzidine

  dine and 1.5899 g (7.8312 mmol) of isochloride

  phthaloyl (Aldrich, recrystallized) in 44 g of acid

  polyphosphoric acid (Aldrich 85%) were mechanically shaken

  and heated under a nitrogen atmosphere as follows: room temperature for 2 hours, 60 C for 2 hours, 110 C for 1 hour, heating at 165 C for 2.5 hours, 165 C for 12 hours and 195 C for 12 hours . During heating, the mixture being polymerized has a dark brown color and is

become viscous.

  The polymer was coagulated in water, neutralized

  5% sodium bicarbonate solution, filtered and washed. Afterwards, it was continuously extracted with methanol for about 16 hours and dried under reduced pressure.

  vacuum 2.6 g of poly-2,2 '- (m-phenylene) - was collected

6.6'-Bibenzothiazole (98%).

  Analysis: C (%) H <%) N (%) S (%) -Calculated for C 2 HNs 2 70,15 2,94 8,18 18, 73

10 2 2

Found: 68.50 3.08 7.69 17.10

Example 19

  Electrochemical Doping of Example 18 A 12.7 cm platinum wire was coated with a thin film of the polymer of Example 18 by immersing the wire in a 2.5% solution of the polymer in methanesulfonic acid. The coated wire of the film was coagulated

  in water, neutralized in a 5% bicarbonate solution

  sodium bonate, washed with water and dried under vacuum at 60 C.

  The polymer coated wire was connected to an Applied Research Apparatus E G and G Princeton comprising a universal programmer and a device

  potentiostatic / galvanostatic with recorder

  the end of the polymer-coated wire was then immersed

  in a 0.1M solution of tetrafluoroborate tetrafluoroborate

  ethylammonium in acetonitrile A sweep of

  A linear current varying from 0 to + 1.8 V relative to the calomel reference electrode was applied to the polymer coated wire. Anode current began to flow when the potential reached + 1.2 V, and a maximum of anodic current was observed at + 1.7V. At this stage, the polymer is positively charged and

  contains tetrafluoroborate anions as compensating dopes

  In fact, the polymer has been rendered electroactive by the application of a potential of approximately + 1.7 V in the presence of an electrolyte solution capable of

  to bring ions of charge compensating dope

  that the direction of the potential sweep has been reversed, a peak of cathodic current has been observed at approximately the same voltage This is the index of an injection

  reversible of an electron previously torn from the polymer.

  This procedure brings the polymer back to its original state

undoped and unfilled.

Example 20

  Preparation of poly-2,2 '- (N-methyl-p, p'-aminodiphenylene) -

  6,6 '-bibenzoxazole Synthesis of the monomer Preparation of N-methyl-4,4'-dicarboxydiphenylamine A one liter three-necked flask equipped with a mechanical stirrer, a reflux condenser, a dropping funnel and a desiccator tube was charged with 272 g of dimethylformamide (3.4 moles) and cooled with ice 160 g (1.05 moles) of PO C 13 were added

  dropwise, followed by 30 g (0.164 mol) of N-

  methyldiphenylamine (Aldrich) The temperature was high

  at 90 ° C and maintained at this value for 118 hours.

  The reaction mixture was quenched in ice and neutralized at pH 6 with sodium hydroxide. The precipitate was filtered off, washed

  and dried giving 28 g of crude product

  silica gel graph and recrystallization in

  ethanol, 18 g of pure dialdehyde were collected.

  Analysis: C (%) H (%) N (%) Calculated for C 15 H 13 O Calculated for C 15 H 13 NO 2 75.30 5.47 5.86 Found: 75.65 5.33 5.87 On prepared Ag 2 O silver oxide by adding 21.4 g of Ag NO 3 in 125 ml of water to a solution of 5.4 g of NaOH in 54 ml of water. Ag 2 precipitate It was filtered off and suspended in a solution of 22.3 g of NaOH in 232 ml of water. 11 g (0.046 mol) of the dialdehyde was added and the mixture was shaken vigorously for 25 minutes. The reaction mixture was filtered, cooled with ice and acidified to about pH 3 with HCl. After filtration and drying,

  obtained 8.9 g (71%) of N-methyl-4,4'-dicarboxydiphenyl-

amine.

  Analysis: C (%) H (%) N (%) Calculated for C 15 H 13 NO 4 67.12 4.73 5.16 Found: 67.02 4.77 5.20 Synthesis of Polymer 1 9984 g (6, 9111 mmol) of r-dihydroxybenzidine dihydrochloride with 1.8737 g (6, 9066 mmol) of N-methyl-4,4'-dicarboxydiphenylamine in 42 g of polyphosphoric acid according to the method.

procedure of Example 19.

  2.52 g (88%) of poly-2,2 '- (N-

  methyl-p, p'-aminodiphenylene-6,6 ') -bibenzoxazole of the following formula: CH 3 to t Analysis: C (%) H (%) N (% calculated for C 27 H 17 N 30278.09 4, 13 10, 12 Found 63.73 3.67 8.13

Example 21

  Electrochemical Doping of Example 20 - A 12.7 cm platinum wire was coated with a thin film of the polymer of Example 20 by dipping the wire into a 5% solution of the polymer in methanesulfonic acid. coated with the film was coagulated in water, neutralized in a 5% solution of bicarbonate

  of sodium, washed with water and dried under vacuum at 60 C.

  The polymer coated wire was connected to a G et Go Princeton Applied Research Apparatus including a universal programmer and a device

  potentiostatic / galvanosatatic with recorder

  The polymer-coated fiber end of the wire was then immersed in a 0.1 M solution of tetraethylammonium tetrafluoroborate in acetonitrile. A linear potential sweep ranged from 0 to + 1.3 V relative to the reference electrode. calomel was applied to the polymer-coated wire Unoanent current began to flow at +0.6 volts, and an anodic current peak was observed at +1.1 volts - this is indicative of an electron wrenching At this stage, the polymer is positively charged and contains tetrafluoroborate anions as dope charge cepensors In fact, the polymer was made electroactive by the application of a potential of about + 1.12 volts in the presence of an electrolyte solution

  capable of supplying charge compensating dope ions.

Claims (17)

  1 electroactive polymer capable of being worked, characterized in that it comprises a charge bearing polymer backbone of diradicals consisting of repeating units of a 5 and 6-membered fused unsaturated ring system whose pentagonal ring   comprises at least one nitrogen atom and a second hetero-   atom chosen from O, S, Se, Te and N substituted, in association with   cation with a sufficient concentration of an ionic dope load compensator.   2 Electroactive polymer according to the claim   1, characterized in that the recurring patterns are   selected from the group consisting of benzimidazoles N-   substituted benzoxazoles, benzothiazoles,   benzoselenazoles, 1-oxazolo [5,4] pyrimidine; 1 oxazolo   / -5,4-b 7 pyridine; thiazolo / -4,5-d 7 pyrimidine; thiazolo / -4,5-d 7 pyridazine; thiazolo / 5,4-d-7 pyrimidine; thiazolo / -4,5-b pyridine; thiazolo / -5,4-b pyrimidine; thiazolo / 4,5-c 7 pyridine; oxazolo / 5,4-c 7 pyridazone; oxazolo / -4,5-b pyridine; oxazolo [4,5-c] pyridine; thiazolo F 5,4,4-c 7 pyridine; oxazolo / -4,5-d 7 pyridazine; thiazolo / 5,4-c 7 pyridazine; oxazolo / -5,4-c-pyridine; thiazolo / 4,5-b 7 pyrazine, their substituted derivatives and their mixtures.   3 Electroactive polymer according to the claim   2, characterized in that the recurring patterns di-   radicals are chosen from the group comprising   N-substituted benzimidazoles, benzoxazoles, benzo thiazoles, and mixtures thereof.   Electroactive polymer according to claim   3, characterized in that the recurring patterns are   related to the polymer chain in the 2.5 or 2.6 positions.   Electroactive polymer according to the claim   4, characterized in that the recurrent patterns   5- and 6-membered condensed rocyclics are intercalated with junction units selected from phenylene, -CH = CH and CH 3 and their mixtures.   6 Electroactive polymer according to one   Claims 4 and 5, characterized in that   the hexagonal nucleus is substituted with a halogen, a   phenyl group or a methoxy group.   Electroactive polymer according to claim   cation 5, characterized in that the ionic compensating   The feedstock is a cation selected from alkali metal ions, alkaline earth metal ions, Group III metal ions, Rxi N +, Rxi + and N + R1. Rxi is a straight chain or chained alkyl group. branched having 1 to 6 carbon atoms, or mixtures of said cations and the polymer-loaded backbone is   selected from the group consisting of a poly-2,2 '- (p-   phenylene) -5,5'-bibenzoxazole, a poly-2,2 '- (p-phenylene) -   , 5'-bibenzothiazole or a poly-2,2 '- (p-phenylene) -1,1' - dimethyl-5,5'-bibenzimidazole.   8 electroactive polymer according to the   cation 5, characterized in that the ionic dope compensates   loader is an anion chosen from the group   comprising As F 4, As F 6, C 1 O 4 PF 6, 503 CF 3, BF 4, NO 3   POF 4, CN, Si F 5, Sb C 16, Sb F 6, H 504, acetate, benzoate, tosylate or mixtures thereof and the polymer-loaded backbone is selected from the group consisting of   poly-2,2 '- (m-phenylene) -6,6' -bibenzoxazole, a poly-   2,2 '- (m-phenylene) -6,6' -bibenzothiazole; a poly-2,2 '-   (m-phenylene) -1,1 ', -dimethyl-6,6' -bibenzimidazole or a   poly-2,2 '- (N-methyl-p, p'-aminodiphenylene) -6,6' -bibenzoxazole.   Electroactive polymer according to claim   cation 5, characterized in that the ionic compensating   The charge generator may be an anion or a cation and the   The polymer-loaded fiber is selected from a poly-2,2 '-   (p-phenylene) -6,6 '-bibenzoxazole, a poly-2,2' - (p-phenylene) -   6,6'-Bibenzothiazole or a poly-2,2 '- (p-phenylene) -1,1' - 6,6'-dimethylbibenzimidazole.   Electroactive polymer, characterized in that it comprises a polymer-loaded backbone in combination with charge compensating ionic dopes, of the formula: ## STR2 ## wherein a is 0 or 1; b is 0 or 1; c is 0 or 1; N is an integer from 1 to 1000; d is an integer from 1 to 2000; S is an integer equal to 1, 2 or 3; R is a 5-membered and 6-membered fused unsaturated diradical ring heterocyclic ring system containing nitrogen; R 'is a fused unsaturated heterocyclic ring system which is the same as or different from R; X 'is a joining pattern; Y 'is the same joining pattern as X'   or a different joining pattern; and M is an ionic dope   than charge compensator, whose electric charge   is opposite to that of the polymer backbone.   Electroactive polymer according to claim   cation 10, characterized in that R and R 'are 2,5-   or 2,6-diradicals of the formula: wherein X is N, and Z is selected from   group consisting of substituted N, O, S, Se, and Te.   12 Electroactive polymer according to the invention   10, characterized in that R and R 'are diradicals of the formula: X y Y / Z wherein Y is a hexagonal ring selected from pyridine, pyrimidine, and pyridazine, X is N and Z is selected   in the group consisting of substituted N, O, S, Se, and Te.   13 Electroactive polymer according to the invention   10, characterized in that R and R 'are di- radicals of formula: R Rii ii NOT   or wherein R 1 is 1 to 3 substituent groups independently selected from H; a disubstituted amino group; an alkyl group having 1 to 4 carbon atoms; an alkoxy group having 1 to 4 carbon atoms; an alkylthio group having 1 to 4 carbon atoms; a cycloaliphatic group having 5 or 6 carbon atoms; an aryl group having 6 to 10 carbon atoms; an aryl group of 6 to 10 carbon atoms substituted with 1 to 3 alkyl groups having 1 to 4 carbon atoms; alkoxy having 1 to 4 carbon atoms, 1 to 3 cyano groups, 1 to 3 halogen atoms, dialkylamino groups having 1 to 4 carbon atoms, a group   alkylthio having 1 to 4 carbon atoms; a het group   nitrogen, pentagonal or hexagonal unsaturated rocyclic, and Riii represents one or two substituent groups selected   independently from the substituent groups for R11.   14 Electroactive polymer according to the invention   13, characterized in that X'-or Y 'is a joining motif selected from the group consisting of the units: * R 1 CH 3 O-; -S-; -NOT-; CH = CH ;;   -C = C-; -CH = CH-CH = CH-; -CH = CH-S-CH = CH-; R 15 δ; S CH = CH-; -CH = CH CH = CH-; R R and -C Rvii CR Vi; Ar-N-Ar-   R is a C 1 -C 6 lower alkyl, aryl, cycloalkyl, or alkoxy group and Rv, Rvi and Rvii represent H or a methyl group, a methoxy group, a halogen   and mixtures thereof, and Ar is a phenylene group or phenylene.   Electroactive polymer according to the   14, characterized in that a and c are 1 and b is 0 and the polymer has the formula: (* Sd) R-X 'n': d   16 Electroactive polymer according to claim   cation 15, characterized in that a is 0, bet c are zero, and the polymer has the formula: 1-x ('Sd) (<Sd)) LIMJ d n-. - i   17 Electroactive polymer according to the invention   16, characterized in that a is zero and the polymer has the formula (+ Sd) (S) R + 11 | d d   18 Electroactive polymer according to the invention   15, characterized in that M is uncation and the polymer is selected from: / \ (-Sd) r + w d or n * 'N (-Sd) +   19 Electroactive polymer according to the invention   15, characterized in that M is an anion and the polymer has the formula: d; or "N 4 <+ Sd) I -I 1 d; or n n   Electroactive polymer according to claim   cation 15, characterized in that M may be an anion or a cation and the polymer has the formula: o 11N N (-Sd) n   21 Electroactive polymer according to claim   cation 17, characterized in that M is a cation and the   1.5 polymer is selected from a polybenzoxazole and a poly- benzothiazole. l d o M